CN102947046A - Processing conditions for manufacturing bioabsorbable stents - Google Patents

Processing conditions for manufacturing bioabsorbable stents Download PDF

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Publication number
CN102947046A
CN102947046A CN2011800286639A CN201180028663A CN102947046A CN 102947046 A CN102947046 A CN 102947046A CN 2011800286639 A CN2011800286639 A CN 2011800286639A CN 201180028663 A CN201180028663 A CN 201180028663A CN 102947046 A CN102947046 A CN 102947046A
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Prior art keywords
laser
processing
polymer
support
microns
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CN2011800286639A
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CN102947046B (en
Inventor
乔尔·哈林顿
瑞安·沃恩
凯文·乔
威廉·皮佩
陈永明
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Abbott Cardiovascular Systems Inc
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Abbott Cardiovascular Systems Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/40—Removing material taking account of the properties of the material involved
    • B23K26/402—Removing material taking account of the properties of the material involved involving non-metallic material, e.g. isolators
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/82—Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/86—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure
    • A61F2/90—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure characterised by a net-like or mesh-like structure
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/82—Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/86—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure
    • A61F2/90—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure characterised by a net-like or mesh-like structure
    • A61F2/91—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure characterised by a net-like or mesh-like structure made from perforated sheet material or tubes, e.g. perforated by laser cuts or etched holes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/82—Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/86—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure
    • A61F2/90—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure characterised by a net-like or mesh-like structure
    • A61F2/91—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure characterised by a net-like or mesh-like structure made from perforated sheet material or tubes, e.g. perforated by laser cuts or etched holes
    • A61F2/915—Stents in a form characterised by the wire-like elements; Stents in the form characterised by a net-like or mesh-like structure characterised by a net-like or mesh-like structure made from perforated sheet material or tubes, e.g. perforated by laser cuts or etched holes with bands having a meander structure, adjacent bands being connected to each other
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/02—Positioning or observing the workpiece, e.g. with respect to the point of impact; Aligning, aiming or focusing the laser beam
    • B23K26/06—Shaping the laser beam, e.g. by masks or multi-focusing
    • B23K26/062—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam
    • B23K26/0622—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam by shaping pulses
    • B23K26/0624—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam by shaping pulses using ultrashort pulses, i.e. pulses of 1ns or less
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/50—Working by transmitting the laser beam through or within the workpiece
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/70—Auxiliary operations or equipment
    • B23K26/702—Auxiliary equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/70—Auxiliary operations or equipment
    • B23K26/702—Auxiliary equipment
    • B23K26/703—Cooling arrangements
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2240/00—Manufacturing or designing of prostheses classified in groups A61F2/00 - A61F2/26 or A61F2/82 or A61F9/00 or A61F11/00 or subgroups thereof
    • A61F2240/001—Designing or manufacturing processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/30—Organic material
    • B23K2103/42—Plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/50—Inorganic material, e.g. metals, not provided for in B23K2103/02 – B23K2103/26

Abstract

The present invention involves laser machining polymer substrates to form a stent with laser parameters that minimize damage to the substrate in a surface region adjacent to the machined edge surface. The wavelength and pulse width are selected for this unique application and they can be controlled to minimize the surface modifications (such as voids, cracks which are induced by the laser-material interaction) which contribute to the variation in mechanical properties with distance from the edge surface, bulk mechanical properties, or a combination thereof.

Description

Treatment conditions for the manufacture of biological absorbable support
Technical field
The present invention relates to Laser Processing tubing to form support.
Background technology
The present invention relates to the Laser Processing such as devices such as supports.Laser Processing refers to that interacting to finish material by laser and target material removes.In general, these processing comprise laser drill, laser cutting and laser grooving, mark or line.The form that Laser Processing is processed with heat energy or photochemical energy is delivered to photon energy in the target material.By melting and blowing away, perhaps by direct boiling/ablation material is removed.
Energy is transferred in the substrate when substrate is lasered.As a result of, the zone beyond the cut edge is modified by energy, and this modification affects this regional character.Generally speaking, the variation of character just is unfavorable for the normal operation at manufactured device.Therefore, expectation is that the energy that reduces or eliminates beyond the material of removing shifts usually, thereby reduces or eliminates size and the modification scope in affected zone.
A kind of application that is used for a large amount of medical applications of Laser Processing comprises makes the endoprosthesis that is radially expanded that is suitable for implanted bodily lumen." endoprosthesis " is corresponding with the Prosthesis who is placed on body interior." inner chamber " refers to the chamber such as the pipe of blood vessel.
This endoprosthesis be exemplified as support.Usually support is as the cylindrical appliance that keeps blood vessel or open and sometimes expand such as other parts of dissecting inner chamber of urinary tract and bile duct.Support is generally used for the treatment of the atherosclerotic stenosis in the blood vessel." narrow " refers to that the diameter in body passage or hole narrows down or shrinks.In this treatment, support is reinforced bodily conduit and is prevented the ISR of the postangioplasty in vascular system." ISR " refers to again occur afterwards narrow at it through obvious successful treatment (such as balloon angioplasty, Stent or valvoplasty) in blood vessel or cardiac valves.
The treatment of using support to carry out diseased region or dysfunction (lesion) relates to sending of support and launches the two." send " and refer to support is introduced and be transported to the zone such as dysfunction in the blood vessel that needs treatment by bodily lumen." expansion " is corresponding to the expansion at the support of the inner chamber inside at area for treatment place.Sending and launching of support finished by following: support is positioned near the end of conduit, this end of conduit is inserted into bodily lumen by skin, propulsion bulb in the treatment site stent, and is removed conduit to expecting treatment position from inner chamber in bodily lumen.
In the situation that balloon expandable stent, support is installed in and is arranged near the supravasal sacculus.Mounting bracket is usually directed to the support compression or presses and hold (crimp) to sacculus.Then by make the support expansion to inflated.Then can recall with this sacculus venting and with conduit.In the situation that self-expanding stent can be fixed to conduit by telescope or sheath with support.When support the expectation body position the time, can recall sleeve pipe so that the support self-expanding.
Support must be able to satisfy a large amount of mechanical requirements.At first, support must can bear structural loads, namely is applied to the compression stress radially on the support when the stent support vascular wall.Therefore, support must possess enough radial strengths and rigidity.Radial strength is the ability of support opposing radial compression force.In case expand, although support may bear various power, comprise the CYCLIC LOADING that is caused by heartbeat, support must fully keep its size and dimension in its whole service life.For example, radial finger to power may tend to cause support inwardly to be shunk back.In general, it is desirable to make shrink back and minimize.
In addition, support must possess that enough flexibilities are held pressing, expansion and CYCLIC LOADING.Support should have enough resistance to fracture so that hold in pressure, expansion and CYCLIC LOADING process medium-height trestle performance can not be adversely affected.
At last, support must be biocompatibility in order to do not cause any bad vascular reaction.
The structure of support normally is comprised of scaffold (scaffolding), and this scaffold comprises style (pattern) or the network of interconnective structural detail, and this structural detail is commonly referred to as in the art and is pillar or lever arm.Scaffold can form by being rolled into columned wire rod, tubing or sheet material.This scaffold is designed such that support can radial compression (holding to allow to press) and is radially expanded (to allow expansion).
Support can be made by the many materials such as metal and polymer that comprise the biodegradable polymer material.Biodegradable support is desired in many treatments are used, in these treatments are used, the existence of support in health may continue the finite time section, until finish the expectation function that it for example realized and kept vascular patency and/or drug delivery.
Can be by making support with Laser Processing at tubing or sheet material formation style.Even the interaction of basic laser-material is similarly, also exist aspect some in dissimilar material (such as metal, plastics, glass and pottery), i.e. different absorption characteristics.In order to produce the result of expectation, it is crucial selecting suitable wavelength.In case selected suitable wavelength, the combination in pulse energy and pulse duration just limits the optimal treatment condition for material type.The character of Biodegradable polymeric such as PLLA and PLGA is tended to that energy is shifted Tathagata and is shifted very responsive from the energy of laser processing.Need interaction that very large effort understands laser parameter and laser-material to select laser system and limit machined parameters helping, make it possible to carry out the faster Laser Processing to the minimized Biodegradable scaffold of adverse effect of character.
Summary of the invention
Various embodiment of the present invention comprises that a kind of Laser Processing substrate to form the method for support, comprising: the thin-walled polymer substrate is provided; Laser beam with the wall that can penetrate this substrate with pulse width and wavelength comes this thin-walled polymer substrate of Laser Processing, the structural detail that has the edge surface through processing with formation, wherein, laser beam makes the substrate modification in the surf zone that is adjacent to the edge surface through processing in very little degree, wherein, this modification comprises so that the crackle that the modulus of polymer changes along with the distance of distance edge surface, space or their combination, and strobe pulse width and wavelength, so that space or crackle are present in the depth that is not more than 2 microns or so that modulus is being not more than 4 microns everywhere convergents.
Other embodiment of the present invention comprises that a kind of Laser Processing substrate to form the method for support, comprising: thin-walled PLLA polymeric substrates is provided; Come Laser Processing thin-walled PLLA polymeric substrates with the laser beam that penetrates described wall, have the structural detail of edge surface through processing with formation, wherein, the pulse width of laser beam and wavelength in green range and described pulse width be 1ps to 10ps.
Other embodiment of the present invention comprises a kind of polymer support body, comprise: a plurality of interconnected structural details, these a plurality of interconnected structural details are to come Laser Processing thin-walled PLLA polymeric substrates to form to form structural detail by the laser beam with transparent walls, wherein, structural detail has and the corresponding sidewall of edge surface through processing, wherein, the surf zone that is adjacent to sidewall has the damage that the interaction by laser beam and substrate causes, wherein, damage is included in crackle or the space that spreads in this surf zone apart from 2 microns of edge surfaces or the less degree of depth.
Description of drawings
Fig. 1 has described support.
Fig. 2 has described to be used for the control system of machine of Laser Processing tubing.
Fig. 3 has described the feature axial view of laser beam with the interactional zone of pipe.
Fig. 4 A has described the pillar that forms by the Laser Processing substrate or the part of structural detail.
Fig. 4 B has described the cross section perpendicular to the part of the pillar of the edge surface through processing.
Fig. 5 to Fig. 8 shows for the combination of pulse width and wavelength and SEM image through the contiguous surf zone of the edge surface of Laser Processing.
Fig. 9 to Figure 13 shows for the modulus of the combination of pulse width and wavelength and relation to the displacement in the edge surface of Laser Processing.
Figure 14 to Figure 17 has described to be illustrated in the situation of various combination of pulse width and wavelength the SEM image through the sidewall surfaces of the support of processing.
The specific embodiment
Embodiments of the invention relate to polymeric substrates are carried out Laser Processing to make the method for support.More specifically, these embodiment relate to selection and are implemented as follows laser system and parameter: this laser system and parameter reduce or eliminate laser to the adverse effect of polymer, and the functional character of reserved materials to greatest extent, such as surface and the block character of polymeric material.
In general, support can have compatible with implanted bodily lumen almost any structure style.Usually, support is comprised of the style of the interconnective structural detail of the longitudinal extension of pillar or lever arm and circumferential hoop or network.Generally speaking, arrange pillar according to following style: this style is designed to contact the internal chamber wall of blood vessel and keeps vascular patency.
Figure 1 illustrates the exemplary configurations of support.Fig. 1 has described the support 10 that is made of pillar 12.Support 10 has the interconnective cylinder ring 14 that connects by link pillar or link 16.Embodiment disclosed herein is not limited to make support or is not limited to support style shown in Figure 1.The present embodiment can easily be applicable to other support styles and other devices.The modification of style structure almost is unrestricted.The external diameter (before pressure is held and launched) of the support of making can be between the 0.2mm to 5.0mm.For application coronarius, the stent diameter of manufacturing is 2.5mm to 5mm.According to application, the length of support can be approximately between the 6mm to 12mm or larger.
The present embodiment is particularly relevant to the Laser Processing polymeric substrates and forms support, yet the method goes for such as metal and ceramic other materials or the composite that is comprised of polymer, metal and ceramic combination.
Polymer can be Biostatic, biological absorbable, biodegradable or biological erodible.Biostatic refer to not biodegradable polymer.Term is biodegradable, biological absorbable erodible and degraded with biology, corrode with absorb can Alternate, and refer to the polymer that when the body fluid that is exposed to such as blood, can be corroded fully or absorb and can little by little be absorbed again, absorb and/or eliminate by health.In addition, drug stent can be by using activating agent or medicine or comprising activating agent or the surface of the Biodegradable polymeric carrier drug delivery medical device of medicine is made.Usually after forming by Laser Processing, medication coat put on rack body or scaffold.This coating usually pillar than scaffold is much thin, and for example, this coating can be 1 micron to 5 microns thickness, and pillar is generally the thickness greater than 100 microns, and for example, 140 microns to 160 micron thick.
Can make implantable medical device such as support to form device by Laser Processing structure or substrate.From the selection area of structure, remove material, so that form the structure of device.Especially, can be by coming processing thin-walled tubular element to make support with laser.Can obtain to have by the selection area that tubing is removed in Laser Processing the support of expectation style.Particularly, can make laser beam in the scanning of the surface of tubing, perhaps can be under this laser beam translation or rotation tubing so that remove groove or the otch that the wall that passes tubing extends always.When the starting point of otch and terminal point meet, drop or remove by assist gas in the zone that otch centers on.Fig. 2 has described the embodiment for the part of the control system of machine of Laser Processing tubing.In Fig. 2, tubing 200 is arranged on for the rotating chuck permanent plant 204 of locating the equipment control device 208 of tubing 200 with respect to laser 212.According to the machine code instruction, tubing 200 is with respect to also being moved axially and rotate by the laser 212 of apparatus control.The material in the tubing is removed on laser selective ground, obtains being cut into the style of tubulose.Therefore, this tubing is cut into the discrete style of finished product support.
Fig. 3 has described laser beam 408 and tubing 414 interactional close-up illustration.Laser beam 408 focuses on the tubing 414 by condenser lens 338.Controlled rotation chuck 337 by at one end and support tubing 414 at the optional pipe supporting pin 339 of the other end.When laser beam cutting and ablation substrate, the refrigerating gas that pass through nozzle 344 outgoing of coaxial gas ejection assemblies 340 guiding coolings through the surface of processing sprays or flows 342.Gas flow also helps from otch to remove near the zone chip and the cooling laser bundle.By arrow 354 gas access is shown.Coaxial gas injection nozzle 344 is centered by focused beam 352.The pressure of the refrigerating gas of supplying with in certain embodiments, is between 30psi and 150psi.The flow velocity of exemplary refrigerating gas is between 2scfh and 100scfh.Exemplary refrigerating gas or processing gas comprise the mixture of helium, argon, nitrogen, oxygen or these gases.
The biodegradable polymer that can be suitable for the application of support scaffold comprises semi-crystalline polymer.Especially, these comprise the polymer that has being about the glass transition temperature (Tg) on 37 ℃ the human body temperature.This polymeric substrates can be made by the composition of independent biodegradable polymer or biodegradable polymer whole or in part, and this biodegradable polymer includes but not limited to: poly-(L-lactide) (PLLA), polymethyl methacrylate (polymandelide) (PM), poly-(DL-lactide) (PDLLA), PGA (PGA) and gather (L-lactide-co-glycolide) (PLGA).For PLGA, it comprises the L-lactide that comprises different mol ratio such as 90:10,75:25,50:50,25:75 and 10:90 and the copolymer of glycolide.
Some character of support are absolutely necessary for carrying out its function, comprise radial strength and resistance to fracture or elongation at break.For example, because when support was held by pressure or launched, support stood significant stress/strain in regional area, so enough resistance to fracture are essential and vital.As shown in Figure 1, when support was held by pressure, inside or the recess area 20 of the bending of support style or bizet 18 stood high compression stress and strain, and when support launched, high compression stress and strain were stood in the outside of bizet 18 or protuberance zone 22.Therefore, pressure hold and the process launched in support be very easy fracture.This fracture may cause the loss of radial strength and expire potential morning and/or the catastrophic failure of support.Therefore, it is vital can keeping the engineering properties of polymer support by the Laser Processing processing.
For the support with desirable properties is provided, can before producing step, introduce its laser radial strength and the resistance to fracture that other treatment step strengthens preformed tubing.For example, by the size in crystallization control territory and by optimizing the best amorphous/crystalline ratio of semi-crystalline polymer, can greatly strengthen fracture toughness; Also can preferentially aim to strengthen radial strength along the hoop direction with tubing by making polymer chain.Be radially expanded step by the heating of on the Tg of polymer, polymer pipe being carried out, can customize the microstructure character of these expectations.For example, it is 65 ℃ to 120 ℃ for the preferred scope of PLLA.On the contrary, the local heat to substrate in laser cutting process can cause the change of the microstructure character expected or the damage of regional area, and this can cause loss or the minimizing of the advantage that the processing by tubing provides.
Laser beam processing is a kind of state-of-the-art noncontact procession technology of using in micron and nanometer manufacturing, controls advanced engineering material, strict designing requirement, the shape of complexity and the needs of unusual size to satisfy.The present invention relates to have in psec (=10 -12) in the scope pulse width (" psec " laser) and have at femtosecond (=10 -15) the laser of pulse width in the scope." pulse width " refers to the duration of time dependent light pulse.Can define the duration in more than one mode.Particularly, the pulse duration can be defined as the full width at half maximum (FWHM) (FWHM) along with the luminous power of time variation.For in the removal that material around is had the material of the accurate amount under the minimum thermal degree of impairment, psec and femtosecond laser provide unique advantage.Generally speaking, picosecond laser has less than the about pulse width of 10ps, and femtosecond laser has the pulse width between 10fs and 800fs.
Two fundamental mechanisms that relate in the laser ablation are considered to photo-thermal and photochemical mechanism.Material is ablated by fusing and vaporization in photo-thermal mechanism, and the photon energy of light is used for directly destroying the chemical bond of polymer in photochemistry mechanism.Atom and the chemical bond between the molecule in substrate are destroyed, cause from the formation of the gaseous material of substrate removal.
The laser ablation of material may occur by heat engine system, non-heat engine system or both combinations in the substrate.For example, than the laser instrument of long pulse mainly by heat engine system from remove materials.In heat engine system, absorbed laser energy causes near the temperature absorption site place and the absorption site to increase, and removes material by fusing or the vaporization of routine.Shortcoming by this mechanism processing is uncut base material generation fire damage.This damage comprises that fusing and thermal diffusion enter in the zone or district of the material of processing edge, and this causes modification and the cut quality problem of the character of the substrate in this zone.
Recently, since the pulse duration less than thermalization characteristic time (that is, reaching the thermally equilibrated time) of typical several psecs, so it is noticeable especially for ablator to have the laser of femtosecond pulse duration.Because much smaller thermal diffusion depth, it is considered to complete or almost entirely non-heat engine system.Picosecond laser mainly is to remove material by non-heat engine system, but also has the heat engine system to a certain degree of some fire damages that are enough to cause substrate for some materials.
More specifically, non-heat engine system relates to the optical breakdown in target material that causes material to be removed.In the optical breakdown process of material, produce very high free electron density, i.e. plasma by the mechanism such as Multiphoton Absorbtion and avalanche ionization.In the situation that optical breakdown, target material is for setting up on the time range too short for the thermal balance from its initial solid-state full-ionized plasma that directly has been transformed into the target material lattice.Therefore, outside the zone of removing, there is insignificant heat conduction.As a result, for having insignificant thermal stress or impact apart from the surperficial approximately 1 micron material in addition through Laser Processing.
Yet, think in the prior art and do not know Fei Re or photochemical mechanism whether can cause to the support performance particularly resistance to fracture the damage of not cutting substrate of adverse effect is arranged.Particularly, and do not know that optical breakdown propagating or infiltration and cause damage in substrate beyond the edge surface of Laser Processing.Do not know whether this damage can affect the character that the support performance is exerted an influence yet.In addition, do not know wavelength, pulse energy and the pulse width of laser parameter when the ablative polymer material such as laser beam and the existence relation of this latent lesion.
We recognize from our research, although the laser ablation PLLA material of the non-heat engine system by using femtosecond laser has negligible fire damage to cutting surfaces, Photochemical effects with injury (space and crackle) below the contiguous surf zone of the edge surface of Laser Processing.These damages reduce the support performance certainly.Therefore, select laser system and its processing parameter for to make in the minimized situation of damage such as the character of resistance to fracture of support for the polymer support be vital making.
Embodiments of the invention comprise the processing parameter that is defined for the picosecond pulse laser system that makes following polymer support, this polymer support tool engineering properties such as radial strength, elongation at break or resistance to fracture with a grain of salt.The laser parameter of control comprises pulse width and the wavelength of laser energy.In Laser Processing, use such parameter to make to be derived from the two the damage of heat and non-heat engine system to minimize.Embodiment comprises that also enforcement laser system and laser system are about being used for making the parameter that has the Laser Processing of minimal damage based on the substrate of PLLA and PLGA.
The inventor recognizes, by can control scope and the degree of depth of the damage that produces by photochemistry mechanism such as the laser parameter of pulse width and wavelength.Generally speaking, the inventor has realized that and have trading off between the damage that produces by heat and non-heat engine system in the polymer of Laser Processing.Just as discussed below, hot and non-heat engine system (that is, photochemistry) the two substrate is all produced damage.Although the feature of damage is different, the two can produce adverse influence to the performance of support.Can adjust laser parameter (for example, pulse width and wavelength) with the minimizing Photochemical effects, but some increases of heat engine system wherein can occur.
For the damage that causes by shorter laser pulse is described, make PLLA support sample by using the laser system in femtosecond and picosecond range.In the block (below on surface) of stent strut, can see the formation in space.Fig. 4 B shows the space and passes the surf zone of cut edge and scatter.
Think a certain amount of gas that some internal solids materials is converted to the formation that causes space or bubble at the high laser energy of cut edge.The space is dispersed in the zone that extends to given depth from the cut edge and surpasses this degree of depth space dissipates.When stent strut in stress lower time, these spaces can be used as and promote the stress concentrator that breaks to form, and therefore, reduce resistance to fracture and reduce elongation at break.Except the space, in sample, usually also observe the crackle in the same area.
Fig. 4 A has described the pillar that forms by the Laser Processing substrate or the part of structural detail 500.Pillar 500 has exocoel surface or outer surface (in the outer surface first being processed of for example tubing) and through the edge surface 508 of Laser Processing.The degree of depth that enters substrate perpendicular to edge surface 508 is illustrated by arrow 510.Fig. 4 B described along A-A perpendicular to the cross section 512 of a part through the pillar 500 of the edge surface 508 of processing.Shown in cross section, this substrate has the depth D of extending to pDiameter be D vSpace or bubble 516.
In addition, measured modulus on the surfacing of support (as the function through the distance of the edge surface of processing of distance support).Observed as the variation of distance through the modulus of the function of the distance at the edge of processing.As shown in Figure 9, along with the increase of distance surface distance, this variation becomes less, and is tending towards converging to the not modulus of the original polymer of Stimulated Light energy affect.The engineering properties in affected zone is comprised that ultimate strength, elongation at break, elastic modelling quantity and maximum load carry out additional testing, and these machinery outputs are subject to adverse effects that the space forms.
The degree of depth that the size in space and space exist depends on the laser parameter such as wavelength and pulse width.The size in space can be less than 1 micron, 1 micron to 2 microns, 2 microns to 5 microns or greater than 5 microns.Crackle or space can appear at and be not more than 2 microns, 5 microns, 10 microns, 15 microns, 20 microns or 30 microns places.Generally speaking, the engineering properties of polymer support can be subject to the impact that these spaces and crackle form, but can alleviate this impact by the suitable selection such as the laser parameter of wavelength and pulse width.
In addition, owing at least two reasons, the heat of base material and non-fire damage depend on the laser energy of given pulse width.At first, the irradiation of laser energy changes with wavelength thoroughly.Secondly, absorption coefficient, or more generally is excited light-struck polymer to the degree of absorption of laser energy, changes with wavelength.Generally speaking, at given wave-length coverage place, absorption coefficient is lower, and is larger in suprabasil fuel factor.For example, the absorption coefficient of PLLA increases and reaches in the about maximum at 300nm to 320nm place from the negligible value at 800nm.Therefore, along with wavelength is decreased to approximately 300nm to 320nm from about 800nm, photochemistry is removed and is increased and heat abstraction reduces.Thereby, because the polymer absorption coefficient depends on the wavelength of laser, so the relative quantity of Fei Re or thermal ablation also depends on the wavelength of laser.
Therefore, the relative quantity of non-heat/thermal ablation depend on pulse width and wavelength the two.In addition, the degree of photochemistry and fire damage the two all depend on pulse width.
As mentioned above, the present invention includes the parameter of adjusting such as pulse width and wavelength, to keep or to keep the engineering properties of support and minimizing or minimize damage to the not cutting part of substrate.This adjustment can be included in ultraviolet (10nm to 400nm) and infrared (〉 700nm) between select one or more wavelength and select one or more pulse widths.In certain embodiments, select wavelength so that polymer in the absorption coefficient at this wavelength place maximum absorbance less than this polymer, for example its absorptivity is 5% to 10%, 10% to 20%, 20% to 40% or 40% to 60% of this maximum absorbance.
In certain embodiments, even the cooling in process has suitable level, also adjust pulse width to avoid excess molten for one or more wavelength.Excess molten may be corresponding to greater than 0.25 micron, 0.5 micron or greater than the molten material of 1 micron thickness.
For given pulse width and wavelength, select average laser power or power (every pulse energy x repetitive rate) and repetitive rate, the wall of polymer pipe cuts substrate so that bundle for example passes all the time in order to sufficiently high energy density (energy of every pulse/spot definition of bundle) is provided.The bundle spot definition is generally 10 microns to 20 microns, but according to application, also can be less than 10 microns or greater than 20 microns.The pulse energy and the energy density (based on 10 microns spot definition) that are used for the laser cutting polymer can be respectively 4 μ J to 200 μ J and 0.5J/cm 2To 200J/cm 2The mean power of every pulse of bundle can reach 0.5W to 4W or surpass 4W.More precisely, power can reach 0.5W to 1W, 1W to 1.5W, 1.5W to 1.8W, 1.8W to 2W, 2W to 2.2W, 2.2 to 2.5W, 2.5W to 2.8W, 2.8W to 3W, 3W to 3.2W, 3.2W to 3.5W, 3.5W to 3.8W, 3.8W to 4W.For the laser of 10ps pulse width, repetitive rate can reach 25kHz to 100kHz, 25kHz to 50kHz, 50kHz to 60kHz, 60kHz to 80kHz or 80kHz to 100kHz.
In addition, adjust in combination or select repetitive rate and refrigerating gas flow velocity (for example, the SCFH(standard cubic foot/hour) the He condition under), so that fuel factor (for example, the fusing at cutting surfaces place) reduces or minimizes and make the cutting speed maximization.Generally speaking, repetitive rate and cutting speed are directly proportional, that is, repetitive rate is higher, and cutting speed is faster, thereby cause the processing time of each support lower.Yet along with the increase of repetitive rate, fuel factor is tending towards increasing.The increase of refrigerating gas flow velocity can be alleviated the fuel factor that causes owing to the repetitive rate increase, thereby allows higher repetitive rate, and then allows higher cutting speed.Therefore, the fastest processing time of selecting repetitive rate and cooling gas flow to have permissible fuel factor with acquisition.
Although bringing fuel factor such as the Laser Processing in 1ps to 12ps or the larger picosecond range, it is favourable for the trade union that adds in this scope, because compare Photochemical effects, fuel factor more can be effectively controlled.As noted above, can be by alleviating fuel factor with refrigerating gas cooling substrate man-hour adding.
Additionally or alternatively, damage is minimized and can minimize corresponding near the thickness of the involved area the edge of Laser Processing that will comprise the space.For example, this regional thickness can less than 2 microns, 5 microns, less than 20 microns or less than 30 microns between.Void area can be 1 micron to 2 microns, 2 microns to 5 microns, 2 microns to 10 microns, 2 microns to 20 microns or 5 microns to 10 microns.Additionally or alternatively, damage is minimized to help to make cutting support along with the modulus change of the distance in the damage field minimizes.Can adjust this parameter to obtain this modulus towards the Fast Convergent of the modulus of not damaging polymer.This modulus can be converged in through processing edge surface less than 4 microns, less than 8 microns or less than 20 microns places.This modulus can be converged between 1 micron to 4 microns, 4 microns to 8 microns or 8 microns to 20 microns of the edge surfaces of processing.This modulus can be converged in apart from 4 microns of edge surfaces or less, 8 microns or less, 15 microns or less or 20 microns or less part through processing.
Additionally or alternatively, by adjusting wavelength and pulse width, can make damage minimize to the engineering properties of the expectation of damage field, for example, ultimate strength, elongation at break, elastic modelling quantity or maximum load.What expect most is that the cutting polymer substrate is maintained and character identical before the Laser Processing of polymeric substrates.
Embodiment also comprises and implements laser system and in the parameter of Laser Processing PLLA substrate when making support.In such embodiments, optical maser wavelength can be in the visible light from 390nm to 800nm.In certain embodiments, the wavelength of laser is in green spectrum or from about 496nm to 570nm or more precisely is 532nm or 515nm.In certain embodiments, pulse width can be 0.8ps or less, 0.8ps to 1ps, 1ps to 5ps, 5ps to 10ps, 10ps to 12ps, 12ps to 15ps or greater than 15ps.As disclosed in example, the inventor is verified, compares with other combination than the small-pulse effect width with wavelength, and the ablation with 10ps laser of wavelength 532nm, repetitive rate 80kHz provides the minimal damage to the PLLA support.In green wavelength or specifically at the 532nm place, the repetitive rate of laser beam can be 25kHz to 100kHz or more precisely be 25kHz to 40kHz, 40kHz to 80kHz or 80kHz to 100kHz.Table 1 provides the laser parameter scope of using in this research.
Table 1 laser parameter
Figure BDA00002557663700111
Below limit and be applicable to herein:
Except as otherwise noted, otherwise all scopes comprise any value in end points and the end points.
Pressure when " radial strength " of support is defined as the distortion that can't retrieve in the support experience.
" stress " refers to the power on the per unit area, as effect by in the plane than the power of zonule.Stress can be divided into the component perpendicular and parallel to the plane, is called normal stress and shear stress.Actual stress represents wherein to record simultaneously the stress of power and area.Be applied to stretch and traditional stress of compression verification is power divided by original gauge length.
" maximum load " or ultimate load are in the situation that the absolute maximum load (power) that the structure that do not lose efficacy can bear.
" intensity " refers to the maximum stress along axis that material will bear before fracture.Come calculating limit intensity by the maximum load that applies at test period divided by original cross-sectional area.
" modulus " can be defined as being applied to the components of stress of per unit area of material or power divided by the ratio along the strain of the axis of applied force that is produced by applied force.Modulus is the initial slope of load-deformation curve, and therefore, determines by linear Hooke (Hookean) zone of curve.For example, material have stretch modulus and modulus of compressibility the two.
" strain " refers to the elongation that occurs or the amount of compression in material under given applied stress or load.
The increase of the length of material that " percentage elongation " can be defined as occurring when being subject to stress.It is typically expressed as the percentage of original length.
" elongation at break " is the strain on the sample when sample ruptures.It is expressed as a percentage usually.
" glass transition temperature " Tg is the amorphous state territory of polymer under the atmospheric pressure temperature when becoming the deformable or extending state of solid from the glassy state of fragility.In other words, Tg is corresponding to the temperature of the beginning of the sub-chain motion that polymer chain occurs.The Tg of given polymer can depend on the rate of heat addition and can be subject to the impact of the thermal history of polymer.In addition, the chemical constitution of polymer has a strong impact on glass transition by affecting mobility.
Example
The example that the below lists and experimental data only are for illustrative purposes, never mean restriction the present invention.Provide following example to help to understand the present invention, still should be appreciated that the present invention is not limited to certain material or the process of example.
Lower group example has been described from the result of PLLA tubing Laser Processing support for seven different parameters combinations of pulse width and wavelength.PLLA tubing is that the extrusion process by the 100%PLLA resin forms.The size of tubing, the size of extruding is: external diameter (OD)=0.0066 inch and internal diameter (ID)=0.0025 inch.According to the processing of before for example in the 12/554th, No. 589 U. S. application, having described, the PLLA tubing of extruding is radially expanded, incorporate this U. S. application into by reference here.Radially expanding the target percentage (%RE) that expands is 400%, and wherein %RE is deformed into 100% * (the original internal diameter-1 of the internal diameter/tubing of expansion tubing).
Seven different parameter combinations of pulse width and wavelength in table 2, have been listed.
Table 2 is used for the not on the same group combination of the pulse width of substrate and wavelength of processing
Group number Pulse width Wavelength (nm) Laser
1 10ps 355 Trumpf 1
2 10ps 532 Lumera 2
3 100fs 266 Libra 3
4 100fs 400 Libra 3
5 100fs 800 Libra 3
6 800fs 1064 IMRA 4
7 800fs 1550 Raydiance 5
1Trumpf?Laser?Technology?of?Fremont,CA
2Lumera?Laser?GmbH?of?Kaiserslautern,Germany
3Coherent,Inc.,Santa?Clara,CA
4IMRA?of?Fremont,CA
5Raydiance?of?Petaluma,CA
In table 3, provide the other laser parameter that is used for operation.Speed is the rate of translation that bundle is striden substrate surface.Passage (pass) is the number of times that repeats to cut style.Processing time is the cutting required time of whole support.The 5th group of Coherent Libra() corresponding to the 800nm in the table 3.Psec (532nm) laser is corresponding to the 2nd group.Laser in table 3 is fixed wave length laser.
Gathering of table 3 laser parameter
Figure BDA00002557663700131
Use some measuring technologies to be evaluated at the character of the surf zone through processing edge.The character that in table 4, has gathered technology and from test, obtained.Use cryoultramicrotome, nano impress and extension test that sample is tested.
Table 4 has gathered the character of method of testing and research
Figure BDA00002557663700142
Cryoultramicrotome refers to the technology for the cutting ultra thin section of microexamination.Cut-out perpendicular to through the processing edge through the slice of machining support and utilize SEM (SEM) to check this slice.Will for not on the same group the space and the degree of depth and the size of crackle compare.Nano impress is used to measure as the substrate modulus of distance through the function of the distance at processing edge.Extension test is used for measuring the engineering properties along the surf zone of the dog hone that comes through the processing edge cuts.
The cryoultramicrotome result
Provide in the table 5 for the gathering of the cryoultramicrotome technology of four combinations of pulse width and wavelength, and Fig. 5 to Fig. 8 shows the SEM image through the adjacent surf zone of finished surface for each combination in the table 5.For the 5th group, the bubble that extends to the degree of depth of 20 μ m shows obvious Photochemical effects.In the 4th group, because the degree of depth of bubble is significantly less than the 5th group, be eased so the low wavelength of comparing with the 5th group presents the Photochemical effects of sening as an envoy to, yet the size of the bubble in the 4th group is larger.With can expect opposite because penetration depth and wavelength be inversely proportional to, so in the 4th group, there is the larger degree of depth.
Table 5 cryoultramicrotome/SEM result gathers
Figure BDA00002557663700151
For the 1st group, crackle is present in the degree of depth of 30 μ m.The 2nd group has four kinds of damages that middle minimum is set; The degree of depth and size that bubble forms are minimum in all test conditions.
Nano impress
In table 6 and Fig. 9 to Figure 13 provided the gathering of nano impress result of five combinations with pulse width and wavelength.Illustrate for the modulus of 16 samples of each combination and the relation between the displacement in the surface at processing edge.In having three combinations that pulse width is 100fs, 800nm sample (the 5th group) demonstrates the fastest convergence.In two combinations of 10ps, the 532nm wavelength has the significantly faster convergence of modulus.The result of 100fs/800nm and 10ps/532nm comparison shows that the rapid convergence of whole modulus is to be provided by the 10ps/532nm wavelength combination.
Table 6 nano impress result gathers
Group number Pulse width/wavelength Observed result Figure
5 100fs/800nm In the approximately depth convergence of 8 μ m 9
4 100fs/400nm - 10
3 100fs/266nm - 11
1 10ps/355nm In the approximately depth convergence of 20 μ m 12
2 10ps/532nm In the approximately depth convergence of 4 μ m 13
Extension test
Sample for the pulse width of utilizing 100ps/800nm and 10ps/532nm/wavelength combination processing carries out the extension test of the surf zone through processing the edge.Use conventional extension test equipment to testing from the dog bone shape sample that through the surf zone of the substrate of Laser Processing, prepares.In table 7 and table 8, provide respectively the test detail for the sample of the sample of 100fs/800nm and 10ps/532nm.
Table 7 uses the description of the extension test sample of 100fs/800nm laser
Sample Vertical dog bone shape
Speed 0.1in/min
Catalogue number(Cat.No.) 19
Thickness 0.0060±0.0002in.
Width 0.0064±0.0002in.
Table 8 uses the description of the extension test sample of 10fs/532nm laser
Sample Vertical dog bone shape
Speed 0.1in/min
Catalogue number(Cat.No.) 16
Thickness 0.0061±0.0001in.
Width 0.0060±0.0001in.
Table 9 has gathered the result of extension test.The most significant nature difference is elongation at break.Compare the sample of 100fs/800nm, the sample of 10ps/532nm has greater than 2.5 times percentage elongation or greater than the percentage elongation of the sample of 100fs/800nm about 60%.Therefore, the sample of 10ps/532nm has significantly higher resistance to fracture.
Table 9 extension test result gathers
Character 100fs/800nm 10ps/532nm Difference percentage *
Ultimate strength (ksi) 12.5±0.7 15.5±0.9 19
Percentage elongation (plasticity) (%) 196±66 496±54 60
Elastic modelling quantity (ksi) 58±4 65±3 11
Maximum load (lb f) 0.49±0.03 0.57±0.04 14
* 100%x(the 3rd row character-secondary series character)/the 3rd row character
The material result gathers
Gathering for the material result of sample group is provided in table 10.The 10ps/532nm sample has best character.
Gathering of table 10 test result
Figure BDA00002557663700171
The quality at the edge through processing
SEM image studies by the observation sidewall through the quality at edge of processing.One of coarse reason is the again deposition of the base material of vaporization.Figure 14 to Figure 17 has described to illustrate the SEM image of the sidewall of the support that uses respectively 100fs/800nm, 100fs/400nm, 10ps/355nm and 10ps/532nm processing.Utilize the sidewall of 10ps/532 combination processing to have the most level and smooth through the processing edge.
Top example shows that the 532nm wavelength provides the optimum balance of cutting speed and fuel factor and Photochemical effects.This method can be applied to the L-lactide of any mol ratio that has between 0 and 1 and poly-(the L-lactide-co-glycolide) of glycolide.The setting of this laser system and laser system also can be applied to cutting metal substrate such as Ta-Nb-W and Co-Cr alloy.
Although illustrated and described specific embodiments of the invention, be apparent that for those skilled in the art, can of the present invention more extensive aspect in do not deviate to make in the situation of the present invention and change and modification.Therefore, claims be intended to will fall in practicalness of the present invention and the scope all these change and modification comprises within the scope of the appended claims.

Claims (13)

1. a Laser Processing substrate comprises to form the method for support:
The thin-walled polymer substrate is provided;
Come the described thin-walled polymer substrate of Laser Processing with the laser beam that penetrates described wall with pulse width and wavelength, have the structural detail of the edge surface through processing with formation,
Wherein, described laser beam makes the described substrate modification in the surf zone that is adjacent to described edge surface through processing in very little degree,
Wherein, described modification comprises the modulus of space, crackle, described polymer along with the variation of the distance of the described edge surface of distance or their combination, and
Select described pulse width and wavelength, so that described space or crackle are present in the depth that is not more than 2 microns or so that described modulus is being not more than 4 microns everywhere convergents.
2. method according to claim 1, wherein, described polymer is PLLA or PLGA.
3. method according to claim 1, wherein, described polymer is PLLA, and described wavelength is 532nm, described pulse width is for being less than or equal to 10ps and more than or equal to 1ps.
4. method according to claim 1, wherein, repetitive rate is 80kHz to 100kHz.
5. a Laser Processing substrate comprises to form the method for support:
The thin-walled polymer substrate is provided;
Come the described thin-walled polymer substrate of Laser Processing with the laser beam that penetrates described wall, have the structural detail of the edge surface through processing with formation; And
Adjust the pulse width of described laser beam and wavelength so that be derived from thermal ablation and the damage to the surf zone that is adjacent to described edge surface through processing of non-thermal ablation minimizes,
Wherein, described minimized damage comprises crackle or the space that is derived from non-thermal ablation and the fusing that is derived from thermal ablation.
6. method according to claim 5, wherein, described polymer is PLLA, and described wavelength and described pulse width are adjusted in the green range and 1ps to 10ps.
7. method according to claim 5 also guides refrigerating gas the location in the described substrate of processing by described laser beam.
8. a Laser Processing substrate comprises to form the method for support:
Thin-walled PLLA polymeric substrates is provided;
Come the described thin-walled PLLA of Laser Processing polymeric substrates with the laser beam that penetrates described wall, have the structural detail of the edge surface through processing with formation,
Wherein, the pulse width of described laser beam and wavelength in green range and described pulse width be 1ps to 10ps.
9. method according to claim 8, wherein, described laser beam causes that crackle or space are formed in the surf zone that is adjacent to described edge surface through processing, the degree of depth in described crackle or space is not more than 5 microns.
10. method according to claim 8, wherein, the modulus that described laser beam causes described polymer is along with the variation apart from the distance of described edge surface, and wherein, described modulus is in the distance convergence less than 10 microns.
11. a polymer support body comprises:
A plurality of interconnected structural details, described a plurality of interconnected structural details are by coming Laser Processing thin-walled PLLA polymeric substrates to form to form described structural detail with the laser beam that penetrates described wall,
Wherein, described structural detail has and the corresponding sidewall of edge surface through processing,
Wherein, the surf zone that is adjacent to described sidewall has the damage that the interaction by described laser beam and described substrate causes,
Wherein, described damage is included in crackle or the space that spreads in the described surf zone apart from 2 microns of described edge surfaces or the less degree of depth.
12. rack body according to claim 11, wherein, described damage also comprises the modulus of described polymer along with the variation of the distance of the described edge surface of distance, and wherein, described modulus is in the distance convergence that is not more than 5 microns.
13. rack body according to claim 11, wherein, described damage also comprises the modulus of described polymer along with the variation of the distance of the described edge surface of distance, and wherein, described modulus is in the distance convergence that is not more than 5 microns.
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